Process for the production of fast



Patented Jan. 2, 1940 PATENT orrlce rnoonss ron m raonuc'rron or ms'r 'rnrrs 0N vncnrsnm mans No Drawing. Application December 15, 1938, Se-

rial No. 116,038. In Switzerland December 19,

8 Claims.

' It has been found that fast tints can be obi tained on vegetable fibers, for instance cotton, ii dyeings or complex metal compounds of direct cotton dyestufis are produced on vegetable fibers, at least one phase of the process being carried out in a caustic alkaline medium at a raised temperature.

By direct cotton dyestuffs are to .be understood those diand polyazo-dyestufis which have affinity for vegetable fibers. Such dyestufis may be constructed from diazotized aromatic amines which impart to the dyestufis an amnity for vegetable fiber for instance cotton and artificial silk from regenerated cellulose, and from any coupling components, for instance phenols, naphthols or amines of the benzene and naphthalene series; or such dyestuffs may be made by coupling any diazotized aromatic amine with a coupling component which imparts to the dyestuif an amnity for vegetable fiber. There may also be used direct cotton dyestuffs derived from diazocomponents which impart to the dyestuffs amnity for vegetable fiber, and alsocoupling components having the same property. The components for the manufacture of the direct cotton dyestufis are selected in such a manner that the dyestufi contains at least one lake-forming group; such components are, for 'example, the diazo-compounds which contain in ortho-position to the diazo-group or in ortho-position or peri-position to a cyclic tertiary nitrogen atom a hydroxyl-, a carboxylor an alkoxy-group or a salicylic acid grouping, or coupling components which contain the salicylic acid grouping as a substituent.

In the foregoing statement it will be seen that for the construction of the direct cotton dyestufis there come into consideration not only the usual aromatic amines of the benzene and naphthalene series which contain lake-forming groups for the purpose of diazo-components and not only the usual phenols, naphthols and amines for the purpose of coupling components but also, in particular, direct-dyeing components, such as, for example, benzidine or stilbene derivatives, diarylazoxy-derivatives and carbazole derivatives, urea and thiourea from arylenediamines, acetoacetic acid derivatives, pyrazolones, aminonaphthols and their sulfonic acids.

The process is of particular value for direct dyeing dyestuffs containing lake-forming groups, the complex metallic compounds of which are sparingly soluble to insoluble in water; to these dyestufis belong those which contain only few or no groups lending solubility, for instance sulfogroups or carboxyl-groups, or which contain such groups lending solubility as, for example, the salicylic acid group, if desired in addition to the suli'o-groups, which groups combine with metal and thereby lose entirely or partly their power of lending solubility.

The production of complex metal compounds of direct cotton dyestufls on vegetable fibers according to the present process may be efiected in such a manner that the fibers are dyed with direct cotton dyestuffs containing groups capable of forming lakes, and the dyeings thus obtained treated with agents yielding metal, the operation being conducted'ln at least one phase of the process in a hot caustic alkaline medium.

The operation of dyeing vegetable fibers with dyestufi's according to this invention may follow the lines usual in applying direct cotton dyestuffs, that is to say the dyeing may be conducted in a bath containing Glaubers salt, preferably also alkali carbonate, for instance sodium carbonate, or the goods may be dyed at a raised temperature in a medium containing caustic alkali, for instance caustic soda or caustic potash.

In many cases, particularly in those in which thedyestufi used affords complex metal compounds which are sparingly soluble to insoluble in water, it is of advantage to bring the dyestuif, before dyeing, for example by grinding, into a fine state of subdivision or/and to dye in presence of a dispersing, wetting or emulsifying agent, that is to say in the presence of anion or cation capillary active substances or such capil lary active substances which are not ionised. Such substances are, for example, organic derivatives of ammonia, for instance amines of the aliphatic, hydroaromatic and aromatic series, which may contain hydroxyl-groups or other substituents, (for example pyridine, amines, alkylamines, ethanolamine, cyclohexylethanolamine, butylethanolamine) sulfonic acids of the benzene andnaphthalene series which contain alkyl-groups, alcohols, for instance glycerine also alcohol sulfonates, soluble condensation products of fatty acids of high molecular weight or of ethylene oxide and amines; oxyoleic acids, sulforicinates, glue, sulfite cellulose liquor, dextrin, albuminous degradation products, for instance protalbinic acid or lysalbinic acid, or organic compounds of high molecular weight, such as the polymerisation products of aldehydes and soluble degradation products of cellulose. In case the dyeing is performed with ence o1, Glaubers salt, and it desired also alkali carbonate, the after-treatment of the dyeing with the agent which yields the metal in complex union, may occur in the same bath or in a fresh bath, in presence of the necessary caustic alkaline medium and at a raised temperature.

When the dyeing with the dyestufi containing the lake-forming group occurs in a caustic alkaline medium at a raised temperature the aftertreatment with the agent yielding the complex bound metal, which may happen in the same or in a fresh bath, may be carried out either by one of the usual methods, for instance by treating the dyeing, if necessary after neutralizing the dyebath in a neutral or acid medium, with the usual agents that yield metal, such as chromium, cobalt, nickel, manganese, aluminium, zinc, vanadium, titanium, and, in particular, copper, or this after-treatment may be applied simultaneously with the dyeing in the caustic alkaline medium at the raised temperature. In this caustic alkalineafter-treatment at the raised temperature, which may occur in presence of the aforesaid dispersing, wetting or emulsifying agent, there are preferably used such agents yielding complex bound metal which are stable to dilute caustic alkalies and correspondingly are only feebly hydrolysed in a caustic alkaline medium or not hydrolysed at all. Such agents are, for example, the aqueous solutions having alkaline reaction which are obtained by mixing the product of the action of an ordinary agent, yielding metal which may contain several metals on an aliphatic hydroxycarboxylic acid (for example lactic acid, tartaric acid, glycollic acid, tartronic acid, mailc acid, dioxytartaric acid, citric acid, saccharic acid, glu conic acid or heptonic acid) or on an amino-carboxylic acid (for example glycocoll) with, for in stance, caustic soda solution, caustic potash solution, ammonia, or a derivative of ammonia, for example ethanolamine, until alkaline reaction is produced.

The production of complex metal compounds of direct cotton dyestufis on vegetable fibers according to the present process may also be eifected in such a manner that the fiber is dyed at a raised temperature with complex metal compounds of direct cotton dyestufis in a caustic al= kaline medium containing, for example, caustic soda or caustic potash lye. These complex metal compounds can be made, with or without the ap- 'plication of pressure, from the aforesaid direct cotton dyestufis containing lake-forming groups in the usual manner, for instance by treatment with an agent yielding chromium, cobalt, nickel, aluminium, manganese, zinc, vanadium, titanium and, in particular, copper, in presence or absence of the usual additions, for example an inorganic salt or acid or an organic salt or acid, with or without application of pressure. Particularly good results are obtained when sparingly soluble to insoluble complex metal compounds are used which may be made in the dye-bath. It is advantageous in many cases that these dyestuffs should be reduced to a finely divided state, that is to say to a highly dispersed form before the dyeing, which is possible, for example, by grinding the dyestufi in the form of a powder or containing a liquid medium, for example in the form oi an aqueous paste, in the usual apparatus, such as a ball-mill or a'roller mill, or by wind sifting; or ii in the metallizing operation there is present, for example an aliphatic hydroxycarboxylic acid or a derivative of ammonia, for instance ethanolamine, or an amino-carboxylic acid, for

instance amino-acetic acid; for in such cases the complex metal compound insoluble in water may pass into solution. These solutions may then be added to thedye-bath, in case the metallizing has not been already carried out in the dye-bath. There may also be added to the dye-bath, together with the agent yielding metal, such an amine or hydroxycarboxylic acid and a complex metal compound or a mixture of this amine or hydroxycarboxylic acid with the complex metal compound obtainable by, for instance, grinding the amine or hydroxycarboxylic acid with the dyestufl. As in the case of dyeing with direct cotton dyestufis containing lake-forming groups, it is also in many cases advantageous, when using the complex metal compounds of the direct cotton dyestuffs, to dye in presence of the aforesaid dispersing, wetting or emulsifying agents.

The dyeings obtained by the process ofthe invention may be developed by treatment, if desired, in a fresh bath for some time with soap or soap and sodium carbonate at about 50-'75 C.

The dyeings obtained are strong colors and are distinguished by advantageous tints'as well as by good iastness, for instance to washing and to light.

The following examples illustrate the invention, the parts being by weight unless otherwise stated and the relationship of parts by weight to parts by volume being that of the kilo to the litre:

Example 1 p 0.075 part of the azo-dyestufi of the formula N=N 0420011 12mm OH ta NH 0311 COOH I OH OH obtainable by coupling 1 mol. tetrazotized 4:4

bers salt, and 10 parts of cotton are entered at 30-40 C. The bath is heated to boiling and dyeing is continued at this temperature for 45 minutes. There are then added to the same bath 20 parts of a caustic alkaline copper solution made by dissolving together 10 parts of crystallized copper sulfate, 12 parts of tartaric'acid and 15 parts 01. caustic soda in 1000 parts of water. The goods are handled for about 30 minutes at -100 C. and then thoroughly rinsed with cold water.

The dyeing obtained is of a considerably purer blue as well as stronger and more level than the dyeing produced from the same dyestufi by the usual after-treatment with a copper compound.

Similar results can be obtained if instead of tartaric acid there is used an equivalent proportion of saccharic acid.

The after-treatment with copper may be conducted also at a lower temperature; indeed, in the cold.

Example 2 0.05 part of the dyestui! of the formula NaN H from 1 mol. tetrazotized 4:4'-diamlnodiphenyland 2 mols. S-methyl-1-hydroxy-benzene-2-carboxylic acid is dissolved in 200 parts of water containing 1.2 parts by volume of caustic soda solution of 30 per cent. strength. To this bath there are added 3 parts of Glaubers salt and 10 parts of cotton are entered at 30-40 C. The bath is heated to boiling and dyeing continued for 45 minutes at 95-100 C. There are then added parts of caustic alkaline solution of copper, made by dissolving 10 parts of crystallized copper sulfate, 12 parts of tartaric acid and 15 parts of caustic soda in 1 litre of water. The goods are handled for about minutes at 90-100" C. and then thoroughly rinsed in cold water.

The dyeing obtained is of better fastness to washing and stronger than that obtained with use of the same dyestufi by the usual after-treatment with copper.

Similar results can be obtained if instead of tartaric acid there is used an equivalent proportion of glycollic acid.

A like result is obtained it the caustic alkaline and 0.1 part of the copper compound of the formula C 0 OH HN H0 NH:

C O on S OIH obtainable in the known manner from 1 mol. tetrazotized 4 4'-diamino-diphenyl'-3 3'-dicarboxylic acid and 1 mol. each of phenyl-2-naphthylamine and 1-amino-B-hydroxynaphthalene- 4-sulfonic acid and made into the form of a HOIS OCH:

I NH HOQN= Qua:

' 0011 cm a 11 pas e with 1.6 parts of caustic soda solution of 30 per cent. strength 0.3 part of tartaric acid and 10 parts of water. and warming for a short time to produce a solution. 10 parts of cotton are then entered, the bath is heated to boiling in the course of half-an-hour and this temperature is maintained for about 1 hour. The goods are then washed thoroughly with cold water. Reddish blue tints of good fastness to washing are obtained.

Similar results can be obtained if instead of tartaric acid there is used an equivalent proportion of glycollic acid amide.

Example 4 fate, as well as 15 parts of water, and then heating for a short time until dissolution occurs. 10

parts of cotton are now entered, the bath is heated to boiling in the course of half-an-hour, and kept at this temperature for about 1 hour. Thorough rinsing with cold water follows. There is obtained a blue dyeing of good fastness to washing.

Similar results can be obtained if instead of tartaric acid there is used an equivalent proportion of malonic acid mono-amide.

Example 5 Into a dye-bathconsisting of 1500 parts of water, 1 part of caustic soda solution of 36 B., 30 parfi of Glaubers salt and 1 part of glycerine, as well as 1 part of the dyestuif described in Example 9, first paragraph of Specification No. 1,861,323, 100 parts of cotton are entered at 30-40- C. The bath is heated in the courseof half-an-hour to 90-100 C. and this temperature is maintained for another quarter of an hour and there is added a solution made by mixing a solution of 0.5 part of copper sulfate and 0.5 part of tartaric acid in 2 parts of water with caustic soda solution until the reaction is 'feebly as to soap the dyeing for hour. A very good orange tint fast to light and washing is obtained.

Similar results can be obtained if instead of tartaric acid there is used an equivalent proportion of ammonium citrate.

Example 6 Into a dye-bath containing 1500 parts of water, 1 part ofcaustic soda solution of 36 B., 30 parts of Glaubers salt and 0.5 part of cane or beet sugar, as well as 1 part of the dyestuff of the formula OCH;

OCH:

CODE

w Dyeing is further continued for 15-20 minutes,

whereupon the goods are rinsed and soaped in a soap bath of per cent. strength and at 50 C. and then rinsed and dried. A blue tint of very good fastness to light and washing is oh- 155 tained.

iii!

Instead of 0.5 part of sugar there may be used 1-2 parts of ethyl alcohol and instead of tartaric acid an equivalent proportion of lactic acid.

If in this example there is substituted for. the

OCH:

ang

I COOH OH: H

dyestufi indicated the tetralrisazmdyestufi oi the formula COOH Hoes cm I HO HQ I coon on: on

2 parts of caustic soda solution of 36 32%., 6 parts of crystallized Glaubers salt and a solution made from 10 parts of water, 0.25 part of crystallized copper sulfate, 0.55 part of potassium sodium tartrate and 3 parts of a caustic soda solution of 40 per cent. strength are entered at 40 C., 20 parts of cotton. In the course of half-anhour the bath is heated to boiling and kept at this temperature for about three-quarters of an hour to 1 hour. The goods are then thoroughly rinsed with cold water and soaped in a fresh bath at 50 C. with 5 grams of Marseilles soap per litre of liquor for about half-anhour.

There is obtained a blue dyeing which is purer, more level, faster to washing and stronger than that obtained by the dyeings produced by the known processes.

Similar results can be obtained if instead of potassium sodium tartrate there is used an equivalent proportion of amino-tartaric acid.

Example 8 Into a dye-bath consisting of 1500 parts of water, 1 part of the dyestuif used in Example 9, first paragraph of Specification No. 1,861,323 and 2 parts of calcined sodium carbonate, 100 parts of cotton are entered at SIB-40 C. The

' NH I on;

on on;

dye-bath is heated to boiling in the course of half-an-hour and there are added 30 parts of Glaubers salt, dyeing being continued for about hour at the said temperature. There is then added to the bath a solution made by mixing an aqueous solution of 0.4 part of chromium sulfate, 0.3 part of nickel sulfate and 0.6 part of tartaric acid with dilute caustic soda solution until the reaction is alkaline and the dyeing is continued for 30 minutes at 90-100 C. Rinslng and drying follow. Orange dyeings are obtained which have good fastness to washing and light.

Similar results can be obtained if instead of tartaric acid there is used an equivalent proportion of tartronic acid.

Example 9 100 parts of cotton are dyed with 1 part of the dyestufi of the formula COOH in 1500 parts of water in presence of 2 parts of calcined sodium carbonate and 30 parts of Glau- I NH I cm H: A H H C H3 0 O H bers salt, the dyeing being continued for /1, hour at 90-100 C. There is then added a solution obtained by mixing a solution of 0.1 part of cobalt hydroxide in 1 part of ammonia of 24 per cent. strength with a caustic alkali solution of SOaH I OCH:

I H OH: 30011 0.4 part of chromium sulfate and 0.3 part of tartaric acid in water. Dyeing is continued for 30 minutes at the raised temperature and the goods are then rinsed, and dried. Fast blue tints are obtained of good fastness to washing and light; they may be improved by a subsequent treatment at 50 C. in a bath containing per litre 2 parts of calcined sodium carbonate as well as 5 parts of soap.

Similar results can be obtained if instead of tartaric acid there is used an equivalent proportion of glycollic acid and instead of ammonia 0.25 part of ethanolamine.

Example 10.

:a solution made from 03' part of copper sulfate,

0.4 part of chromium sulfate and 0.6 part of tartaric acid, with caustic soda solution until the reaction is caustic alkaline. Dyeing is continued further for 30 minutes at 90-100" C. and the goods are rinsed and dried. Fast yellow tints are obtained, the fastness to washing of which may be subsequently improved by treatment in a soap bath or a soda-soap bath.

Similar results can be obtained if instead of tartaric acid there is used an equivalent proportion of malic acid.

Example 11 Into a dye-bath consisting of 700 parts of water, 0.2 part of the dyestufi of the formula:

are then added to the dye-bath 20 parts of an alkaline solution of copper made by dissolving 10 parts of crystallized copper sulfate, 12 parts of tartaric acid and 15 parts of caustic soda in 1000 parts of water. Dyeing is continued for a further 30 minutes at 95-100 0., and the goods are thoroughly rinsed with cold water and soaped as usual. There is obtained a green-blue dying faster to light and of a greener tone than a dyeing produced with use of the same dyestufi by the known processes.

Similar results are obtained when caustic soda solution is used in the dye-bath instead of sodium noQm coon on;

2 parts of caustic soda solution of 36 36. and 6 25 parts of crystallized Glaubers salt are entered 20 parts of cotton at 30 C. In the course of half-an-hour the bath is heated to boiling and i kept at this temperature for about hour to 1 hour. There is then added to the dye-bath a so- 30 lution made by mixing a solution of 0.25 part of a The blue-dyeing thus obtained is purer, more level and faster to washing and stronger than that obtained by the known processes.

Similar results can be obtained if instead of potassium sodium tartrate there is used an equivalent proportion of sodium gluconate.

Example 12 A dye-bath is prepared from 200 parts of water at 30-40 C., 0.2 part of calcined sodium carbonate, 3 parts of Glaubers salt and 0.075 part of the azo-dyestufi of the formula HO NH:

O CH:

HO NH:

OzH

from tetrazotized 4 :4 -diamino-3 3'-dimethoxydiphenyl (1 mol.) and l-amino-B-hydroxynaphthalene-4-sulfonic acid (2 mols), 10 parts of cotton are entered, the bath is heated to boiling in the course of half-an-hour and dyeing is continued for 45 minutes at this temperature. There :8 N N B i d-NH l 0cm N=N NmQon H H cm coon carbonate, or if an equivalent proportion of lactic acid is used instead of tartaric acid.

Example 13 A dye-bath is prepared from 200 parts of water of temperature -40" 0., 3 parts of Glaubers.

salt and 0.1 part of the azo-dyestufi from 1 mol. of tetrazotized 4 4'-diaminostilbene-3 3' -dicarboxylic acid and 1 mol. each of 2-phenylaminonaphthalene and 5:5 -dihydroxy-2 :2 -dinaphthylamine-7:'7'-disulfonic acid, 10 parts of cotton are entered, the bath is heated to boiling in the course of half-an-hour and kept at this temperature for about 45 minutes. The material is then well rinsed and then treated for half-anhour at 60-70 C. in a fresh bath with 20 parts of a caustic alkaline solution containing in 1000 parts by volume of 10 parts of crystallized copper sulfate, 12 parts of tartaric acid and 21.4 parts of caustic soda. There is obtained a fast blue dyeing.

Example 14 A dye-bath is prepared from 200 parts of water of temperature 30-40 0., 3 parts of Glaubers salt and 0.1 part of the azo-dyestuff from 1 mol. of tetrazotized 4:4-diaminostilbene-3:3- dicarboxylic acid and 1 mol. each of 2-phenylaminonaphthalene and 5:5'-dihydroxy-2:2'-dinaphthylamine-7:7'-disulfonic acid, 10 parts of cotton are entered, the bath is heated to boiling in the course of half-an-hour and kept at this temperature for about 45 minutes. There arethen added to the dye-bath 20 parts of a caustic alka-" line copper solution containing in 1000 parts by volume 10 parts of crystallized copper sulfate, 12 parts of tartaric acid, 15 parts of caustic soda and 10 parts of a solution of ammonia of 24 per cent. strength. Dyeing is continued for about '30 minutes at 95-100 0., and the material is then rinsed with cold water, soaped if necessary and dried. There is obtained a fast blue dyeing.

Similar results can be obtained if instead of tartaric acid an equivalent quantity of saccharic acid is used.

Example 15 A dye-bath is prepared from 200 parts of water of temperature 30-40? (7., 3 parts of Glaubers saltand 0.1 part of the azo-dyestuff from 1 mol. of tetrazotized 4:4'-diaminostilbene-3:3'-dicarboxylic acid and 1 mol. each of 2-phenylaminonaphthalene and 5:5-dihydroxy-2:2-dinaphthyiamine-7:'I'-disulfonic acid, 10 parts of cotton are entered, the bath is heated to boiling in the course of half-an-hour and kept at this temperature for about 45 minutes. There are then added to the dye-bath 0.2 part of the sodium salt of the sulfonated condensation product from benzyl chloride and naphthalene and 20 parts of a caustic alkaline copper solution containing in 1000 parts by volume 10 parts of crystallized copper sulfate, 12 parts of tartaric acid and 15 parts of caustic soda. Dyeing is continued for about 30 minutes at 95-100 C. and the material is then rinsed with cold water, scaped if necessary and dried. There is obtained a fast blue dyeing.

Similar results can be obtained if instead of tartaric acid there is used an equivalent quantity of glycoilic acid, or if instead of the sodium salt of the sulfonated condensation product from benzyl chloride and naphthalene there is used 0.2 part of the sodium salt of sulfophthalic acid diamyl ester.

Example 16 A dye-bath is prepared from 200 parts of water at 30-40" C., 3 parts of Glauber's salt and 0.1 part of the azo-dyestufl obtained by coupling 1 mol. of tetrazotized 4:4'-diaminodiphenyl-3:3'- dicarboxylic acid with 1 mol. each of 2-phenyiaminonaphthalene and l-amino 8 hydroxynaphthalene-i-sulfonic acid, 10 parts of cotton are entered, the bath is heated to boiling in the course of half-an-hour and dyeing is continued for 45 minutes at this temperature. There are then added to the dye-bath 20 parts of an alkaline copper solution containing in 1000 parts by volume 10 parts of crystallized copper sulfate, 12 parts of tartaric acid and 15 parts of caustic soda. Dyeing is continued for about 30 minutes at 95-l00 C. and the material is then thoroughly rinsed with cold water, scaped in known manner and dried. There is obtained a reddish-blue dyeing which is faster to alkali than one produced by the usual process of after-treatment with copper.

Similar results can be obtained if instead of tartaric acid there is used an equivalent quantity of glycollic acid or/and if instead of copper sulfate there is used an equivalent quantity of nickel sulfate.

Example 17 A dye-bath is prepared from 200 parts of water at 30-40" C., 3 parts of Glaubers salt and 0.25 part of a paste of 35 per cent. strength of the azo-dyestufi of the formula COOH GOOH

COOH 0H COOH from tetrazotized 4z4'-diaminodiphenyl-3:3'-dicarboxylic acid and 1-(4'-hydroxy-3'-carboxy)- phenyl-S-methyI-S-pyrazolone, 10 parts of cotton are entered, the bath is heated to boiling in the course of half-an-hour and dyeing is continued for 45 minutes at this temperature. There are then added to the dye-bath 20 parts of an instead of tartaric acid an equivalent quantity of aminotartaric acid and/or instead of copper sulfate an equivalent quantity of nickel sulfate.

Example 18 A dye-bath is prepared from 200 parts of water at 30-40 C., 3 parts of Glaubers salt and 0.25 part of a paste of 35 per cent. strength of the azo-dyestufl' from tetrazotized 4:4'-diaminodiphenyl-3:3'-dicarboxylic acid and 1-(4-hydroxy 3' carboxy-) phenyl-3-methyl-5-pyrazolone, 10 parts of cotton are entered, the bath is heated to boiling in the course of half-an-hour and dyeing is continued for 45 minutes at this temperature. There are then added to the dyebath 20 parts of an alkaline copper solution containing in 1000 parts by volume 10 parts of crystallized copper sulfate, 12 parts of tartaric acid, 15 parts of caustic soda and 10 parts of a solution of ammonia of 24 per cent. strength. Dyeing is continued for about 30 minutes longer at 95-100 C., and the goods are thoroughly rinsed with cold water and dried. There is obtained a very fast red-brown dyeing.

Similar results can be obtained if there is used instead of tartaric acid an equivalent quantity of glycollic acid and/or instead of copper sulfate an equivalent quantity of nickel sulfate.

Example 19 A dye-bath is prepared from 200 parts of water at 30-40 C., 3 parts of Glaubers salt and 0.25 part of a paste of 35 per cent. strength of the azo-dyestuif from tetrazotized 4:4'-diaminodiphenyl-3:3'-1dicarboxylic acid and 1-(4'-hydroxy 3 carboxy-)phenyl-3-methyl-5-pyrazolone, 10 parts of cotton are entered, the bath is heated to boiling in the course of half-an-hour and dyeing is continued for 45 minutes at this temperature. There are then added to the dyebath 0.2 part of an emulsifying agent prepared from glue and soap and 20 parts of an alkaline copper solution containing in 1000 parts by volume 10 parts of crystallized copper sulfate, 12

parts of tartaric acid and 15 parts of caustic soda. Dyeing is continued for about 30 minutes longer at 95-100 0. and the material is then thoroughly rinsed with cold water, if necessary scaped in the usual manner and dried. There is obtained a fast red-brown dyeing which alters less when washed than a dyeing which has been after-coppered according to known processes.

Similar results can be obtained if there is used instead of tartaric acid an equivalent quantity of glycollic acid and/or instead of copper sulfate an equivalent quantity of nickel sulfate.

Example 20 For dyeing 100 parts of cotton-satin a dyebath of temperature C. is prepared from 4000 parts of water and 2.5 parts of the copper compound of the dyestufi of the formula the wetted cotton is introduced and in the course of hour the temperature is raised to 95 C.; 30 parts of crystallized Glaubers salt are now added and dyeing is continued for 30 minutes longer at 95 C. There is then added to the dyebath an alkaline solution prepared by mixing aqueous solutions of 1.5 parts of crystallized-copper sulfate 1.2 parts of potassium tartrate and 0.6 part of caustic soda. Dyeing is continued for 30 minutes longer at -95 C. and the material is then rinsed with cold water. There is obtained a powerful brown dyeing which is fast to light and to washing. The dyeing is brighter, considerably stronger and of better fastness to alkali than one which has been after-treated with copper sulfate in a fresh bath according to known methods. a

Similar results are obtained if instead of potassium tartrate an equivalent quantity of glycollic acid amide is used.

Example 21 For dyeing 100 parts of cotton-satin a dyebath of temperature 50 C. is prepared from 4000 parts of water and 2.5 parts of the dyestuff of the formula the wetted cotton is introduced 'and in the course of "A; hour the temperature is raised to C.; 30 parts of crystallized Glaubers salt are now added and dyeing is continued for 30 minutes longer at 95 C. There is then added to the dyebath an alkaline solution prepared by mixing aqueous solutions of 1.5 parts of crystallized copper sulfate, 1.2 parts of potassium tartrate and 0.6

part of caustic soda. Dyeing is continued for.

Example 22 For dyeing parts of cotton-satin a dye-bath of temperature 50 C. is prepared from 4000 parts of water and 2.5 parts of the dyestuff of the formula the wetted cotton is introduced and in the course HOOC of A hour the temperature is raised to 95 0.;

30 parts of crystallized Glaubers salt are now added and dyeing is continued for30 minutes longer at 95 C. There is then added to the dyebath an alkaline solution prepared by mixing aqueous solutions of 1.5 parts of crystallized copper sulfate, 1.2 parts of potassium tartrate and 0.6 part of caustic soda. Dyeing is continued for 30 minutes longer at 90-95 C. and the material is then rinsed with cold water. There is obtained a powerful yellow dyeing which is fast to light and to washing. The dyeing is considerably stronger and of better fastness to alkali than one which has been after-treated with copper sulfate in a fresh bath according to known methods.

Similar results are obtained if instead of copper sulfate an equivalent quantity of nickel sulfate is used; instead of potassium tartrate there may be used an equivalent quantity of sodium saccharate.

Example 23 For dyeing 100 parts of cotton-satin a dye- .bath of temperature 50 C. is prepared from 4000 parts of water and 2.5 parts of the dyestuff of the formula I OCH:

- COOH 90-95 C. and the material is then rinsed with cold water. There is obtained a powerful yellow dyeing which is fast to light and to washing. It is considerably stronger and of better fastness to alkali than a dyeing obtained by after-treatment with copper sulfate in a fresh bath according to known processes.

Similar results are obtained if instead of copper sulfate an equivalent quantity of nickel sulfate is used, and if instead of potassium tartrate an equivalent quantity of sodium glycollate is used.

Example 24 0.075 part of the azo-dyestuff obtained by coupling 1 mol. of tetrazotized 4:4'-diamino stilbene-3:3'-dicarboxylic acid on the one side with 1 mol. of phenyI-Z-naphthylamine and on the other side with 1 mol. of 5:5'-dihydroxy-2:2'- dinaphthylamine-7:7'-disulfonic acid, is dissolved in 200 parts of water. 1.2 parts by volume of caustic soda solution of 30 per cent. strength and 3 parts of Glaubers salt are added and 10 parts of cotton are entered at 30-40 C. The temperature of the bath is raised to boiling and dyeing is continued for 45 minutes at this temperature. The bath is then neutralized by addition of 0.86 part by volume of acetic acid of 84 per cent. strength, 0.2 part of crystallized copper sulfate is added in the form of an aqueous solution and the goods are handled in the bath for about 30 minutes at 90-100" 0., rinsed and dried. There is obtained a blue dyeing of good properties of fastness.

Similar results can be obtained by using instead of 0.2 part of crystallized copper sulfate an equivalent quantity of neutral sodium copper tartrate.

Example 25 0.075 part of the azo-dyestuflz obtained by coupling 1 mol. of tetrazotized 4:4'-diaminostilbene-3:3'-dicarboxylic acid on the one side with 1 mol. of phenyl-2-naphthylamine and on the other side with 1 mol. of 5:5'-dihydroxy-2:2- dinaphthylamine-7:7'-disulfonic acid, is dissolved in 200 parts of water. 1.2 parts byvolume of canstic soda solution of 30 per cent. strength and 3 parts of Glaubers salt are added and 10 parts of cotton are entered at 30-40 C. The temperature of the bath is raised to boiling and dyeing is continued for 45 minutes at this temperature. The bath is then neutralized by addition of 0.86 part by volume of acetic acid of 84 per cent.

' strength, 0.2 part of crystallized nickel sulfate is added in the form of an aqueous solution and the goods are handled in the bath for about 30 minutes at -100 C., rinsed and dried. There is obtained a blue-violet dyeing of good properties of fastness.

Example 26 0.075 part of the azo-dyestufi obtained by coupling 1 mol. of tetrazotized 4:4'-diaminostilbene- 3:3'-dicarboxylic acid on the one side with 1 mol. of phenyl-2-naphthylamine and on the other side with 1 mol. of 5:5'-dihydroxy-2:2'-dinaphthylamine-7:7'-disulphonic acid, is dissolved in 200 parts of water. 1.2 parts by volume of caustic soda solution of 30 per cent. strength and 3 parts of Glaubers salt are added and 10 parts of cotton are entered at 30-40" C. The temperature of the bath is raised to boiling and dyeing is continued for 45 minutes at this temperature. Then there are added to the same bath 20 parts of a caustic alkaline copper solution obtained by dissolving 10 parts of crystallized copper sulfate, 6.08 parts of glycollic acid and 15 parts of caustic soda in 1000 parts of water. The goods are thoroughly rinsed with cold water. There is obtained a blue dyeing of good properties of fastness.

Similar results are obtained by using tartaric acid amide instead of glycollic acid.

Example 27 A dye-bath is prepared from 200 parts or water at 30-40 C., 0.6 part by volume of caustic soda solution of 30 per cent. strength, 3 parts of crystallized Glaubers salt and 0.8 part of the copper compound of the azo-dyestufl. used in Example 22, 10 parts of cotton are entered, the bath is raised to boiling in the course of half-an-hour and dyeing is continued for about hour at 90-100 C. The goods are then thoroughly rinsed with cold water and dried. There is obtained a fast yellow dyeing.

Similar results can be obtained by using the nickel compound of the dyestufl instead of the copper compound.

Example 28 A dye-bath is prepared from 200 parts of water at 30-40 C., 0.6 part by volume of caustic soda solution of 30 per cent. strength; 3 parts of crystallized Glaubers salt and 0.8 part of the copper compound of the azo-dyestufl used in Example 22 as well as 0.5 part of protalbinic acid, 10 parts of cotton are entered, the bath is raised to boiling in the course of half-an-hour and dyeing is continued for about hour at 90-100 C. The goods are then thoroughly rinsed with cold water and dried. There is obtained a fast yellow dyeing.

Similar results can be obtained if instead of protalbinic acid an equivalent quantity of lysalbinic acid is used.

Example 29 A dye-bath is prepared from 200 parts of water at 30-40" C., 0.6 part by volume of caustic soda solution of 30 per cent. strength, 3 parts of crystallized Glaubers salt and 0.8 part of the copper compound of the azo-dyestufl. used in Example 23, 10 parts of cotton are entered, the bath is raised to boiling in the course of half-an-hour and dyeing is continued for about hour at 90-100 C. The goods are then thoroughly rinsed with cold water and dried. There is obtained a fast yellow dyeing.

Similar results can be obtained by using a copper-chromium compound oi the dyestufl' instead of the copper compound.

Example 30 A dye-bath is prepared from 200 parts of water at 30-40 C., 0.6 part by volume of caustic soda solution of 30 per cent. strength, 3 parts of crystallized Glaubers salt and 0.8 part of the copper compound of the azo-dyestufi used in Example 23, as well as 0.5 part of an oxyoleic acid such as Monopole soap, 10 parts of cotton are entered. the bath is raised to boiling in the course of halfan-hour and dyeing is continued for about A hour at til-100 0. The goods are then thoroughly rinsed with cold water and dried. There is obtained a fast yellow dyeing.

Similar results can be obtained by using a sulforicinate instead of the Monopole soap.

Example 31 A dye-bath isprepared from 400 parts of water at 30-40 C. and 0.25 part of the chromium- .10 copper compound prepared in known manner from-the dyestuif of the formula.

parts of cotton are entered and the temperature is raised to 95 C. in the course of Y hour; then 3 parts of crystallized Glauber's salt are added and dyeing is continued for 30 minutes longer at 95 C. There is then added to the same dye-bath a caustic alkaline-solution prepared by dissolving in water 1.5 parts of crystallized copper sulfate, 1.2 parts of potassium tartrate and 0.6 parts of caustic soda. Dyeing is continued for 30 minutes longer at 90-95 C. and the goods are then rinsed with cold water and dried." There is obtained a grey dyeing fast to light and to washing. It is brighter, has a more greenish hue and is faster to washing than a dyeing obtained by dyeing the material directly with the same chromium-copper compound; it is also faster to washing than a dyeing obtained by after-treating the same chromium-copper compound with copper sulfate in a fresh bath by the usual processes.

sam le 32 A dye-bath is prepared from 400 parts of water -is continued for 30 minutes longer at 95 C.

so There is then added to the same dye-bath a caustic alkaline solution prepared by dissolving in water 1.5 parts of crystallized copper sulfate, 12'

parts of potassium tartrateand 0.6 part of caustic soda. Dyeing is continued for 30 minutes longer at 90-95 C. and the goods are then rinsed with cold water and dried. There is obtained a grey dyeing fast to light and to washing. It has a more greenish hue and is faster to washing than a dyeing obtained by dyeing the material directly with the same chromium compound; it is also faster to washing than a dyeing obtained by after-treating the azo-dyestuif with copper sulfate in a fresh bath by the usual processes.

What we claim is:

1. Process for the production'of fast tints on vegetable fibers, comprising producing dyeings of complex metal compounds of direct cotton dyestufis on vegetable fibers, wherein at least once in the course of the dyeing process the vegetable 7 fibers are treated in a caustic alkaline medium areaoos on I N: 50'}! ErN OH NO H H NC:

at a raised temperature not exceeding the boiling point of the said medium.

2. Process for the production of fast tints on begetable fibers, comprising dyeing the fibers with direct cotton dyestufls containing lakeforming groups, and treating the dyeings with agents yielding metal, wherein at least once in the course of ,the dyeing process the vegetable fibers a e treated in a caustic alkaline medium at a re, ed temperature not exceeding the boiling point of the said medium.

3. Process for the production of fast tints on vegetable fibers, comprising dyeing the fibers with complex metal compounds of direct cotton dyestufis in a caustic alkaline medium at a raised temperature not exceeding the boiling point of the said medium.

4. Process for the production of fast tints on vegetable fibers, comprising dyeing the fibers with direct cotton dyestuifs containing lake-forming groups, of which the complex metal compounds are sparingly soluble to insoluble in water and in dilute alkalies, and treating the dyeings with agents yielding metal, wherein at least once in the course of the dyeing process the vegetable fibers are treated in a caustic alkaline medium at a raised temperature not exceeding the boiling point of the said medium.

5. Process for the production of fast tints on vegetable fibers, comprising dyeing the fibers with complex metal compounds of direct cotton, dyestuffs in a caustic alkaline medium at a raised temperature not exceeding the boiling point of the said medium, the said complex metal compounds being sparingly soluble to insoluble in water and in dilute alkalies.

6. Process for the production of fast tints on vegetable fibers, comprising dyeing the fibers with complex metal compounds of direct cotton dyestufis in a caustic alkaline medium containing compounds selected from the group consisting of ammonia and organic derivatives of ammonia, at a raised temperature not exceeding the boiling point of the said medium, the said complex metal compounds being sparingly soluble to insoluble in water and in dilute alkalies.

7. Process for the production of fast tints on vegetable fibers, comprising dyeing the fibers with direct cotton dyestuffs containing lake-forming groups, of-which the complex copper compounds are sparingly soluble to insoluble in water and in dilute alkalies, and treating the dyeings with agents yielding copper stable towards dilute alkalies, wherein at least once in the course of the dyeing process the vegetable fibers are treated in a caustic alkaline medium at a raised temperature not exceeding the boiling point of said medium. .5

8. Process. for the production of fast tints on vegetable fibers, comprising dyeing the fibers with complex copper compounds of direct cotton dyestuifs in a caustic alkaline medium at a raised temperature not exceeding the boiling point of the said medium, the said complex metal compouii'dsT'being sparingly soluble to insoluble in water and in dilute alkalies.

FRITZ STRAUB.

WALTER HANHAR'I. WALTER ANDERAU. 

